Esters of blown hydroxy acetylated ricinoleic acid compounds with oxyalkylated phenol aldehyde resins



Patented 1 Jan. 8, 1952 ESTERS OF BLOWN HYDROXY ACETYLATED RICINOLEIC ACID COMPOUNDS WITH OXYALKYLATED P HE N O L ALDEHYDE RESIN S Melvin De Groote, St. Louis, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, DeL, a corporation of Delaware 3 a No Drawing. Application December 10, 1948,

SerialNo. 64,445

The present invention is concerned with certain new chemical products, compounds or compositions, having useful applications in various arts. This invention is a continuation-in-part of Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil," emulsified 11 Claims. (Cl. 260-19) 2 oil," etc., and which comprise fine droplets of naturally-occurring waters of brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the our co-pending application, Serial No. 734,201, 5 emulsion. This specific application is described filed March 12, 1947, and now abandoned. It inand claimed in our co-pending application, Serial eludes methods or procedures for manufacturing 0- fi ed De be 1943, HOW Patent said new products, compounds or compositions, No. 2,541,991, issued February 20, 1951. See also as well as the products, compounds or composiour co-pending application, Serial No. 64,469, filed tions themselves. Said new compositions are 10 December 10, 1943- esters in which the acyl radical is that of the The new products are useful as wetting, deterfatty acid of a drastically-oxidized hydroxyacetgent and levelling agents in the laundry, textile ylated ricinoleic compound selected from the class and dyeing industries; as wetting agents and deconsisting of castor oil, triricinolein, diricinolein, I tergents in the acid washing of building stone and monoricinolein, superglycerinated castor oil, casbrick; as wetting agents and spreaders in the aptor oil estolides, polyricinoleic acid, and ricinoleic plication of asphalt in road building and the like; acid, and the alcoholic radical is that of certain as a flotation reagent in the flotation separation hydrophile polyhydric synthetic products; said f v rio q s p ns c t in n hydrophile synthetic products being oxyalkylat ve y charg d particles such as Sewage, c0941 tion products of (A) an alpha-beta alkylene oxide Washing waste water, and various trade wastes having not more than 4 carbon atoms and selected and the like; as r ci insecticides. emulsifrom the class consisting of ethylene oxide, proili agents, a e p for cosmetics, Spray pylene oxide, butylene oxide, glycide and methyl- 011$, Water-repellent textile finishes; a lubriglycide, and (B) an oxyalkylation-susceptible, cents, t fusible, organic solvent-soluble, water-insoluble The oxyalkylated resins, u d o p d the phenolaldehyde resin; said resin being derived by alcoholic radical of the new esters, are decribed reaction between a difunctional monohydric phen 11 Patents 2,499,370, granted March 7, 1950, 1101 and an aldehyde having not over 8 carbon and granted February 20, 1951, and atoms and reactive toward said phenol; said reserence is made .to those patents for a description in being formed in the substantial absence of triso of the o d y e r s u ed a th r yfunctional phenols; said phenol being of theforalkylat n to p odu th a h l p ts For mula specific examples of the resins, reference is made OH to Examples 1a through 103a of Patent 2,499,370.

For examples of the oxyalkylated products, refer- R ence is made to Examples lb through 18b of Patent 2,499,370 and to the tables which appear in columns 51 through 56 thereof, and also is made in which R is a, hydrocarbon radical having at 130 the tables which appear at columns 31 through least 4 and not more than 12 carbon atoms and 46 of Patent 2,541,991. The drastically oxidized substituted in the 2, 4, 6 position; said oxyalkyl- 40 h r y yl d riciholeic c p u whic ated resin being characterized by the introduction provide the acyl radicals of the new esters are into the resin molecule of a plurality of divalent scribed in deta in Pa t 2,373,223, an d radicals having the formula (mom, in which R1 Apr 5, and reference is m de to that p is a member selected from the class consisting of ent for a description of these products. For speethylene radicals, propylene radicals, butylene cificexamples of these products, reference is made radicals, hydroxypropylene radicals, and hyto the examples under the heading Drasticallydroxybutylene radicals, and n is a numeral varyoxidized hydroxyacetylated castor oil, Examing from 1 to 20; with the proviso that at least D 6 1 through appearing on p 3 Of t s P 2 moles of alkylene oxide be introduced for each ent. phenolic nucleus. It will be noted that having obtained a compound which is essentially a polyhydric alcohol, i. e., an oxyalkylated resin of the type herein contemplated. one can produce esters by any one of the various procedures employed for producing 56 esters of detergent-forming acids of the common yl or ethyl ester of the selected acid or selected drastically-oxidized hydroxyacetylated compound in presence of the alkaline catalyst so as to eliminate methyl or ethyl alcohols. Trans-esterification or cross-esterification can be employed in connection with a glyceride, such as the use of drastically-oxidized hydroxyacetylated castor oil, with the formation of glycerine, which, under conditions of reaction, probably polymerize to give polyglycerols, and thus gives 'a' significant and many times a major proportion of the desired ester. As to a rather complete review of the preparation of polyhydric alcohol esters of fatty acids, see Chemical Review, 33, 257-349 (1943).

Example 12 An acidic drastically-oxidized hydroxyacetylated ricinoleic acid carboxyl is obtained in the manner described in Patent 2,373,228, or by some obvious modification thereof. For instance, ricinoleic acid, diricinoleic acid, or triricinoleic acid or a mixture thereof, is subjected to hyd'roxyacetylation and then to drastic oxidation. Ihe product is analysed to determine its acid value. An alternate procedure is to employ a drasticallyoxidized hydroxyacetylated ricinoleic acid compound and subject it to acid saponification so as to yield the corresponding fatty acids. .lin any event, an oxyalkylated derivative, such as Example 10Gb of Patent 2,541,991, is esterified with a drastically-oxidized hydroxyacetylated ricinoleic acid compound in acidic form in an amount sufficient to convert approximately one-fourth of the polyglycol radicals into the fatty acid ester. The hydroxyl value of the oxya-lkylated derivative can be calculated without determination, based on the hydroxyl value and weight of the phenol-alde; hyde resin originally employed, plus the increase in weight after oxyalkylation. If glycide or methylglycide is employed, allowance must be made for the polyhydric character of the oxyalkylating reactant. In any event, if desired, the hydroxyl value of the oxyalkylated product can be determined by the Verley-Biilsing method, or any other acceptable procedure. The esterification reaction is conducted in any conventional manner, such as that employed for the preparation of the higher fatty acid esters of phenoxyethanol. v

The fatty acids of the kind described, 1. e.,

drastically oxidized hydroxyacetylated fatty acids, show at least some solubility in the oxyalkylated derivatives of the kind shown in the previous examples, even though this is not necessarily true of the glycerides of the fatty acids. In this instance, reference is made to the oxyalkyl ated derivatives in absence of a solvent. Since esterification is best conducted in a system, it is our preference to add xylene or even a higher boiling solvent such as mesitylene, cymene, tetra;- lin, or the like, and conduct esterification in such consolute mixture. It is not necessary to add all the fatty acid at one time. One may add a quarlter or half the total amount to be esterified, and after such portion of the reactant has combined, then add more of the specifically described fatty acid. The solubility of the specifically, described fatty acid, of course, increases as the hydroxyl also true if one resorts to trans-esteriflcation or cross-esterification with the glyceride or low molal alcohol ester.

Our preference is to have present a substantial amount of xylene or higher boiling water-insoluble solvent, and to distill under a reflux condenser arrangement, so that water resulting from esterification is volatilized and condensed along with the xylene vapor in a suitably arranged trap. The amount of xylene employed is approximately equal to one-half the weight of the mixed reactants The water should be removed from the trap, either manually or automatically and the xylene returned continually for further distillation. Such reaction-is hastened if a small amount of dry hydrochloric acid gas is continuously injected into the e'sterification mixture. When the "reaction is completed, the xylene is removed by distillation. Small amounts of unreacted specifically described fatty acid can be be converted into the methyl or ethyl ester and removed by vacuum distillation, or permitted to remain. For example, an excess of anhydrous ethyl alcohol may be added, and reacted so as to esterify any residual specifically described fatty acid, and then such excess of ethyl alcohol may be distilled off as a alcohol-5% of water mixture, and thus, the water resulting from esterification with the alcohol can be removed.

However, even where the amount of specifically described fatty acid employed is stoichiometrically equal to the hydroxyl radicals present, we have not found it desirable to take any undue precautions to eliminate any residual specifically described fatty acid. As a matter of fact, numerous examples, including the present one and those subsequently described, yield partial or fractional esters in which there are present residual hydroxyl radicals. Under such circumstances there are substantially no free fatty acid radicals present and the products obtained by partial esterification instead of complete esterification, represent the most valuable type. A sulfonic acid, such as toluene sulfonic acid, may be added in amounts of /2 to 1% to act as a catalyst.

The following ratios illustrate the specific examples.

Grams Xylene-containing 'oxyalkylated resin 10Gb of Patent 2,541,991 a 776 Product identified as drastically oxidized hydroxyacetylated castor oil, Example 1 of Patent 2,373,228 248 Xylene Para-toluene sulfonic acid 10 The above mixture was placed in a reflux vessel with appropriate condenser, and refluxed at a temperature of to C. for approximately 4 to 6 hours, but in any event until the amount of water was at least equal to theoretical (4.5 cc.). Our experience has been, however, that due to moisture in the components or due to etherization, or for some other reason, the yield of water is apt to be at least 16% or 15% higher by the time the reaction has gone to completion or equilibrium.

The oxyalkylated resins vary from tacky solids tolthick, viscous liquids, and the color varies from a light amberalmost water-white-to a dark or blackish color, particularly a reddishblack in the case of resins obtained using furfural or benzaldehyde. Fatty products obtained by oxidation are usually reddish-amber in color.

radical is replaced by an ester radical; This 15 Sometimes they maybe even darl; amber in color.

They are generally yiscous liquids, apt tobe tacky and sometimes show a consistency just'short of the sub-rubbery stage. The esters obtained are apt to show physical properties, as far as viscosity and color go, somewhat intermediate between the same properties of the initial reactants. At times, they may beeven more viscous in body and darkor in appearance than either reactant. Part of this added darkening is the result of the sulfonic acid catalyst employed. In a general way, this characterizes allthe subsequent esters described,

as-far as properties go, when the solvent is ref moved; We generally remove a small amountof the sample, evaporate the solvent on a steam bath overnight, and examine the residue. For most applications; particularly breaking of oil field emulsions, the color is immaterial and there is no real advantage in" removing the solvent. For this reason no further comment will be di rected to these particular properties.

Example 26 Patent 2,373,228 n '533 Xylene 110 Para-toluene sulfonic acid 11 The amount of water eliminated was 9 cc. or slightly in excess thereof.

Example 3c The same procedure was followed as in Example 1e, preceding, except that the amount of described, drastically-oxidized' hydroxyacetylated ricinoleic acid compound fatty acid employed was sufiicient .to convert three-fourths of the polyglycol radicals into ester form. Specifically, the following ratios were employed:

Grams Xylene-containing oxyalkylated resin 1155 of Patent 2,541,991 685 Product identified as drastically oxidized hy- 'i' droxyacetylated castor oil, Example 3 of j Patent 2,373,228 858 Xylene 125 Para-toluene sulfonic acid 2.5

The amount of water eliminated was 14 cc. or slightly in excess thereof.

Example 46' Grams Xylene-containing oxyalkylated resin 1171) "of Patent 2,541,991 1075 Product identified as drastically oxidized.

Xylene 150 Paratoluene sulfonic acid 15 The amount of water eliminated was 19.8 cc. I

Example 5e The same procedure was followed as in Examples 1e to 4e, preceding, except that the oxy- 'alkylated derivative, instead of-being the kind exemplified in the above examples, was a resin exemplified by Example 12Gb of Patent 2,541,991. Specifically, the following ratios were employed:

Grams of Patent 2,541,991 -1 Product identified as drastically oxidized hydroxyacetylated castol oil, Example 3 Xylene-containing oxyalkylated resin 12 -".ofPate'nt 2,373,228 1140 X'y1ene- 150 Para-toluene 'sulfonic acid The amount of water eliminated was slightly in excess of 18cc.

Example 6c The same procedure was followed as in Examples 1e to 46, preceding, except tht the oxyalkylated thermoplastic phenolaldehyde resin was one of the type exemplified by Examples 1341) o to138b of Patent 2,541,991. Specifically, the following ratioswere employed:

, Grams Xylene-containing oxyalkylated resin 13Gb of Patent 2,541,991 818 Product identified as drastically oxidized hydroxyacetylated castor oil, Example 2 of Patent 2,373,228 1065 Xylene 150 Para-toluene sulfonic'acid 15 The amount of water distilled off was slightly in excess of 19 cc.

Example 7e The same procedure was followed as in the preceding examples except that the reaction was conducted by means of the ethyl or methyl ester, instead of a corresponding acid. The ethyl or methyl ester can be obtained in any one of various ways. The previous description includes the hydroxyacetylation of the ethyl or methyl ester of ricinoleic acid, diricinoleic acid, or triricinoleic acid, followed by drastic oxidation. A procedure equally suitable is to obtain a similar derivative from the glyceride, to wit, a product of the kind described under the previous headings, Examples 1a to 4d of Patent 2,541,991. Such product can be converted into the methyl or ethyl ester by the usual alcoholysis procedure employing anhydrous methyl alcohol, or anhydrous ethyl alcohol, and a catalyst such as an alkaline material. -.Such procedure is conventional; see, for example, U. S. Patent No. Re. 22,751, reissed April 30, 1946, to Trent, In such procedure, the liberated glycerol is discarded. We prefer to use the methyl or ethyl ester obtained by the transposition of a drastically-oxidized, hydroxyacetylated triricinolein. The reaction involving the second transposition with the, oxyalkylated thermoplastic resin is 7 preferably conducted in the absence of, any solvent, or if a solvent be employed, it should be fairly high'.boiling, such as xylene. Instead of using an acid catalyst, an alkali such as caustic soda or sodium inethylate is employed. The amount ii's'ed'variesfroni' one' te'nth' of1% to'1%".'

,An average value may be in the neighborhood of one-half of 1%. The reaction is conducted preferably with'the methyl 'ester'which results in the elimination of methanol. In the presence of asolvent-such as xylene, the methanol might distill over with the xylene, and if so, can be removed by washing with water, followed by removal of any moisture from the xylene with subsequent return of the xylene to the reaction vessel. However, any suitable procedure and any suitable catalyst may be employed so as to form the ester by elimination of a low molal alcohol. particularly methanol. It is to be noted that by varying the amounts of the methyl ester added to the oxyalkylated resin,;one can introduce varying proportions of the acyl radical just as readily as if the acid itself were employed. It is intended, ofcourse, to contemplate an entire range of such compounds comparable to those previously described. Obviously, completeness of reaction can be determined in any one of a number of ways, such as determination of the amoimt of low molal alcohol volatilized.

As a specific example, the following ratios were used:

Grams Xylene-containing oxyalkylated resin 14Gb of Patent 2,541,991 T11 Methyl ester corresponding to product of drastically oxidized hydroxyacetylated castor oil, Example 1 of Patent 2,373,288- 503 Xylene 125 Sodium methylate 5 The above mixture was refluxed for approximately 4 to 6 hours. At the end of this time the entire amount of xylene present in the mixture was removed by distillation. The xylene so obtained was washed with water and the decrease in volume noted. This decrease in volume represented methanol. proximately grams, a small fraction of which was obtained from the sodium methylate.

In the preparation of a similar derivative, the

following ratios were employed:

Grams Xylene-containing oxyalkylated resin 14211 of Patent 2,541,991 1158 Ethyl ester of the product identified as drastically oxidized hydroxyacetylated castor oil, Example 2 of Patent 2,37 3,22 1095 Xylene 125 Sodium methylate 6 The same procedure was followed as previously,

except that ethanol was Washed out from the xylene. The amount of water-soluble alcohol removed was approximately grams, part of which represented methanol from the sodium methylate.

Example 8e The amount removed was apall below the point ofpyrolysis, as far as the oxyalkylated derivative or fatty acid compound is concerned. As a rule, pyrolysis may take place at any temperature above 250 C. We prefer to conductv the reaction by simply employing derivatives'of the kind described under the headings, drastically oxidized hydroxyacetylated'castor oil, Examples lto 4 of Patent 2,373,228 inelusive, and mix such reactants with the approe priate amount of oxyalkylated resins of the kind described, so that if reaction is complete and all the acyl groups originally attached'to the glycerol radical become transposed to the polyglycerol radical, then by using variations of reactarits, one will obtain the same range as describedunder the previous headings of Examples le to 6e, preceding.

Specifically, the following example will serve as an illustration:

. Y mGrams. Xylene-containing oxyalkylated resin 1102) of Patent 2,541,991 686 Product identified as drastically oxidized hydroxyacetylated castor oil, Example 2 of Patent 2,373,228 1065 Sodium methylate 5 Xylene The above mixture was heated under an air condenser with constant stirring for approximately 6 hours at 145 to C. Except for the evolution or a small amount of methyl alcohol or moisture there was no distillate for the reason that the alcohol liberated, i. e., glycerol, is non-volatile.

In reactions of this kind with the liberation of a non-volatile alcohol, it is quite likely the reaction does not go to completion. However, the equilibrium apparently permits a significant or substantial yield, due in part to the fact that the glycerol forms polyglycerols with comparative ease, whereas the hydroxyl radicals of the oxyalkylated derivatives may etherize to a lesser degree. There is also the possibility that in part the glycerol may etherize with the oxyalkylated derivative. This brings about the same result as if the oxyalkylated derivative had been treated with a mole of glycide as a terminal reactant.

One rather peculiar property is the fact that Where some of the oxyalkylated resins show moderate or limited solubility in water prior to esterification, particularly in the manner last indicated, they sometimes seem to show even greater solubility in water after such esterification process, notwithstanding the fact that apparently a large hydrophobe radical is introduced, and in essence, the repetitious alkylene oxide linkage apparently must solubilize both hydrophobe radicals. i. e., the one derived from the resin and the one derived from the detergent-forming monocarboxy acid.

The solubility of the esters shows variation of substantially the same kind shown by the oxyethylated resins except, as a rule, any esterification tends to decrease solubility in water (subject to the exceptional instances noted in the preceding paragraph) and perhaps to a. lesser extent in polar solvents tends to increase solubility in organic solvents particularly in nonpolar organic solvents. This is obvious insofar that the esters herein contemplated need not be total esters but may be fractional as Well. Thus, the range of esters includes such wide variations in composition and solubilities'.

As has been pointed out previously the esters monoricinolein,

as prepared in previous examples usually have a solvent, such as xylene or the like, present. Our preference is to leave such solvent present when the products are employed for demulsification or similar purposes. Needless to say, the

solvent can be eliminated by evaporation or distillation, including vacuum distillation. If-desired, the final product. can be neutralized with ammonia or caustic potash or caustic soda to the methyl orange "end point so as to eliminate the acidity due to any sulfonic acid employed as a catalyst. If desired, any residual carboxyl acidity can be eliminated by further neutralization.

Attention is directed to the following fact. The

oxyalkylated resins herein used as intermediate materials for further reaction to provide more complex derivatives are characterized by having certain minimum hydrophile properties as described, and it is particularly desirable that'these emulsion when mixed with xylene in the manner have an altered hydrophobe-hydrophile balance.

If an ester is prepared from a high molal acid, hydrophile character is increased. If such ester is prepared from sulfo benzoic acid or the like, the hydrophile character may be enhanced. This is also true in even more complicated derivatives, such as the introduction of a quaternary nitrogen atom radical. In the formation of esters, the hydrophobe-hydrophile balance is effected by the factor of whether one prepares a complete or partial ester. In a general way, although the herein described compounds are valuable for various purposes, particularly demulsification, even though the hydrophobe character may be increased somewhat and the hydrophile character decreased, yet when the same test is applied to the derivatives as is applied to the oxyalkylated resins and when such derivatives also show at least some minimum hydrophile character, they are unquestionably most advantageous, particularly for use as demulsifiers. Thus, in the hereto appended claims in pointing out the invention in such specific character, at least part of the claims are directed to the derivative in which the derivative meets the same final test in regard to the production of a xylene emulsion. Stated another way, the final derivative must be at least as hydrophile or more so than the minimum requirement for the oxyalkylated resin as defined.

We claim:

1. An ester in which the acyl radical is that of the fatty acid of a blown hydroxyacetylated ricinoleic acid compounds selected from the class consisting of castor oil, triricinolein, diricinolein, superglycerinated castor oil, castor oil estolides, polyricinoleic acid and ricinoleic acid, and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta .alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble,

inc formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (Rlo)n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylgroup reactive toward said phenol; said resin beeneradicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus. 7

2. An ester in which the acyl radical is that of consisting of castor oil,'triricinolein, diricinol'ein,

monoricinolein, superglycerinated castor oil, castor oil estolides, polyricinoleic acid and ricinoleic acid, and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyethylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (C2H40)n; wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus, and with the final proviso that the hydrophile properties of said ester, as well as said oxyethylated resin, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

3. An ester in which the acyl radical is that of the fatty acid of a blown hydroxyacetylated ricinoleic acid compound selected from the class consisting of castor oil, triricinolein, diricinolein, monoricinolein, superglycerinated castor oil, castor oil estolides, polyricinoleic acid and ricinoleic acid; and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide;

and (B) an oxyethylation-susceptible, fusible,

Organic solvent-soluble, water-insoluble, lowin which R is an aliphatic hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroiwls of a plurality of divalent radicals having the formula (C2H4O)n; wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said ester, as well as said oxyethylated resin, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution shaken vigorously with one to three volum s of wate f1. The product of claim 2 wherein R is sub- Vstituted in the para position.

5. The product of claim 2 wherein R is a butyl radical substituted in the para position.

6. The product of claim 2 wherein R is an amyl radical substituted in the para position.

7, The product of claim 2 wherein R is a nonyl radical substituted the para position.

8. The product of claim 3 wherein R is substituted'in the para position.

9. The product of claim 3 wherein R is a butyl radical substituted in the para position.

10. The product of claim 3 wherein R is an amyl radical substituted in the para position.

11. The product of claim 3 wherein R is a nonyl radical substituted in the para position.

MELVIN DE GROOTE. BERNHARD KEISER.

No references cited 

1. AN ESTER IN WHICH THE ACYL RADICAL IS THAT OF THE FATTY ACID OF A BLOWN HYDROXYACETYLATED RICINOLEIC ACID COMPOUNDS SELECTED FROM THE CLASS CONSISTING OF CASTOR OIL, TRIRICINOLEIN, DIRICINOLEIN, MONORICINOLEIN, SUPERGLYCERINATED CASTOR OIL, CASTOR OIL ESTOLIDES, POLYRICINOLEIC ACID AND RICINOLEIC ACID, AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO; SAID PHENOL BEING OF THE FORMULA 